Hydrophilic polymer coatings with durable lubricity and compositions and methods thereof

ABSTRACT

The invention provides a novel hydrophilic polymer and latex polymer blend coating formulation and compositions thereof, and their use on various devices (e.g., prophylactic and medical devices) to form hydrophilic and flexible coatings with durable lubricity.

PRIORITY CLAIMS AND RELATED PATENT APPLICATIONS

This application claims the benefit of priority to PCT/US2017/051783,filed Sep. 15, 2017, which claims the benefit of priority to U.S.Provisional Application Ser. No. 62/408,625, filed on Oct. 14, 2016, theentire content of each of which is incorporated herein by reference inits entirety.

STATEMENT REGARDING FEDERALLY FUNDED RESEARCH OR DEVELOPMENT

This invention was made with government support under Grant No.R43HD089856-01A1 awarded by the Eunice Kennedy Shiver Nation Instituteof Child Health and Human Development Center of the U.S. NationalInstitute of Health. The Government has certain rights in the invention.

TECHNICAL FIELD OF THE INVENTION

The invention generally relates to polymer formulations and use thereofin surface coatings of various products. More particularly, theinvention relates to a novel hydrophilic polymer and latex polymer blendcoating formulation and compositions thereof, and their use on variousdevices (e.g., prophylactic and medical devices) to form hydrophilic andflexible coatings with durable lubricity.

BACKGROUND OF THE INVENTION

Natural or synthetic latex possesses favorable physical and rheologicalproperties due to its soft elastic characteristics and high resistanceto mechanical stresses and heat. Because of these desirable properties,latex is widely incorporated in a number of consumer goods and medicaldevices (e.g., condoms). Due to its hydrophobicity, however, latex isnot compatible with blood, and can irreversibly adsorb proteins andplatelets on its surface when in contact with biologics. Additionally,high frictional and abrasive forces can occur between the interface oflatex-based medical devices and tissues, leading to discomfort,increased risks of infections, tissue damage, and pain for the user.

According to the World Health Organization, the lack of adequatelubrication remains a major drawback for proper and consistent condomuse. The minimal amount of lubrication included with condoms duringpackaging is typically insufficient to maintain the condom's lubricitythroughout intercourse. Consequently, partners will either (1) not use acondom and increase risks for unwanted pregnancies and spread ofSexually transmitted infections (STIs), or (2) use an inadequatelylubricious condom resulting in mucosal microtrauma, pain, and decreasedsatisfaction between partners. This microtrauma and pain may arise fromdramatically increased penetrative force during intercourse whenlubrication is inadequate. Typical healthy vaginal lubrication has beenreported to require a penetrative force of 0.5 kg, whereas a typicalpost-menopausal or poor vaginal lubrication requires a three-foldgreater penetrative force of 1.5 kg. There is also a significant demandfor better lubrication products and strategies to be used with condoms,particularly for older women in menopause and post-menopausal stagesaffected by vaginal dryness.

Silicone-based lubricants are the most commonly used lubricants todayand are applied to both male and female condoms during the manufacturingprocess prior to packaging. Despite this, condom consumer satisfactionwith condom lubricity remains low. Unfortunately, these unmet needsexacerbate the societal stigma and negative perception that condoms areuncomfortable and will decrease pleasure during intercourse, whichadversely affects the consistency of proper condom usage.

A variety of methods have been explored to chemically or physicallymodify natural or synthetic latex to possess hydrophilic and lubricousproperties, all with limited success. The different types of hydrophilicmonomers that are compatible for polymerization reactions are currentlylimited. Surface modification strategies involving the application ofhydrophilic coatings to the surface of latex-based substrates haveproven to be challenging, for example, due to persistent delaminationbetween the coating and latex.

Thus, there is an ongoing critical need to develop novel durable,flexible, non-toxic and low-costing hydrophilic coatings and applicationstrategies that are compatible with natural and synthetic latex-basedsurfaces and medical devices, particularly for condoms.

SUMMARY OF THE INVENTION

The invention is based in part on the unexpected discovery of a novelhydrophilic polymer and latex polymer blend coating formulation, andcompositions thereof, that are suitable for use on various devices(e.g., condoms and other prophylactic or medical devices) to formhydrophilic and flexible coatings with durable lubricity.

A key feature of the invention is that, when in contact with water or anaqueous solution, the hydrophilic coating becomes slippery with durablelubricity, resulting in lowered frictional forces when in contact withtissue or other interfaces. This thin hydrophilic coating is able tomaintain its lubricity continuously when in contact with surfaces in thepresence of water without impacting on the mechanical and physicalproperties of the coated device.

In one aspect, the invention generally relates to an aqueouscomposition, which comprises: a hydrophilic polymer; a suspension oflatex polymer microparticles; and, optionally, one or more ofvulcanizing or accelerating agents. The hydrophilic polymer has a meanmolecular weight in the range from about 1 kDa to about 10,000 kDa andis present in the composition at a concentration from about 2 w/v % toabout 10 w/v %. The latex polymer microparticles are present in thecomposition at a concentration from about 20 w/v % to about 60 w/v %.The weight ratio of the hydrophilic polymer to the latex polymermicroparticles is in the range from about 1:1 to about 10:1.

In another aspect, the invention generally relates to a compositionformed by mixing: a first aqueous solution of a hydrophilic polymer witha concentration in the range from about 1 w/v % to about 20 w/v %; and asecond aqueous suspension of latex polymer microparticles with aconcentration in the range from about 20 w/v % to about 65 w/v %. Thehydrophilic polymer has a mean molecular weight in the range from about1 kDa to about 1,000 kDa. The volume ratio of the first aqueous solutionto the second aqueous suspension is in the range from about 1:1 to about1:3.

In yet another aspect, the invention generally relates to a curedmaterial formed by heating a composition disclosed herein for a timesufficient to form interpenetrating polymer networks of crosslinkedhydrophilic polymer and latex polymer. The process results in thephysical entrapment of the hydrophilic polymer on the latex surface uponthe heat curing process. Interpenetrating polymer networks can reinforceand improve the properties of the resulting polymer matrix. This curingprocess can also include but is not limited to using chemical reagentsto form the polymer network.

In yet another aspect, the invention generally relates to a latexcondom. The latex condom includes: a sheath of an elastomeric materialselected from natural or synthetic rubber latex, the sheath having anouter surface and an inner surface; and a layered coating comprising afirst or base layer disposed on and adhered to at least a portion of theouter surface of the sheath and a second or top layer disposed on andadhered to at least a portion of the first or base layer. The first orbase layer is a cured latex polymer. The second or top layer is a curedblend of a latex polymer and a hydrophilic polymer having a meanmolecular weight in the range from about 1 kDa to about 1,000 kDa,wherein the weight ratio of the hydrophilic polymer to the latex polymeris in the range from about 10:1 to about 1:10.

In yet another aspect, the invention generally relates to a packagedcondom product comprising one or more latex condoms disclosed herein.

In yet another aspect, the invention generally relates to a method formanufacturing a condom. The method includes: providing a sheath of anelastomeric material selected from natural or synthetic rubber latex,the sheath having an outer surface and an inner surface; depositing afirst layer of an aqueous suspension of a latex polymer to at least aportion of the outer surface of the sheath; curing the latex polymerwith exposure to heat for a time sufficient to form a first or baselayer of cured latex polymer; depositing a second layer of acomposition, comprising a hydrophilic polymer and a suspension of latexpolymer, to at least a portion of the first or base layer; and curingthe second layer of hydrophilic polymer and latex polymer with exposureto heat for a time sufficient to form a second or top layer. Thehydrophilic polymer has a mean molecular weight in the range from about1 kDa to about 1,000 kDa and is present in the composition at aconcentration from about 2 w/v % to about 10 w/v %. The latex polymermicroparticles are present in the composition at a concentration fromabout 20 w/v % to about 65 w/v %. The weight ratio of the hydrophilicpolymer to the latex polymer microparticles is in the range from about1:1 to about 10:1.

In yet another aspect, the invention generally relates to a condommanufactured by a method disclosed herein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1. Coating application onto condoms using a dip-coating approach. Aglass mandrel is dipped into a latex barrel to form the first or baselayer that is cured with heat. This is followed by a second dip into thehydrophilic and latex polymer blend barrel and is followed by heat tocure onto the base layer to from the coated condoms.

FIG. 2. Modifications and fixtures made to accommodate the hydrophilicand latex polymer blend coating application on latex condoms to theirstandard dip-coating equipment under GMP-like conditions. (Left)Schematic of one dip-coating fixture on their automatic instrument;(Right) the hydrophilic and latex polymer blend formulation was preparedin container.

FIG. 3. Hydrophilic and latex polymer blend-coated condoms showedsimilar thickness when compared to a standard lubricated condom, whichwere measured using a digital micrometer as according to ISO 4074.(Right) Hydrophilic and latex polymer blend-coated condoms can withstanda minimum of 18 L and 1 kPa of air in airburst testing.

FIG. 4. Insertion apparatus using male masturbator for friction studies.(Right) Coating durability study of hydrophilic and latex polymerblend-coated condoms in comparison to Lifestyles, Durex, and Trojanlubricated condoms in the presence of water. Hydrophilic and latexpolymer blend-coated condoms showed consistently low frictional forceseven up to 500 insertions (blue) whereas all commercially availablesilicone-lubricated condoms broke even before 100 insertions.

FIG. 5. Coating durability study of hydrophilic and latex polymerblend-coated condoms (green) to non-lubricated condoms (grey) with 0.5mL of water-based personal lubricant, 0.5 mL of silicone-based personallubricant, 0.5 mL of water.

FIG. 6. Scanning electron microscopy (SEM) images (Left) at 10 μmresolution and Atomic Force Microscopy (AFM) images (Right) of (A.)non-coated and (B.) hydrophilic and latex polymer blend-coated latexsurfaces.

FIG. 7. Example of a hydrophilic and latex polymer blend-coated condomwith baby powder that has been rolled-up (left) and packaged in foiled(right).

DEFINITIONS

Unless stated otherwise, or implicit from context, the following termsand phrases include the meanings provided below. The definitions areprovided to aid in describing particular embodiments, and are notintended to limit the claimed invention, because the scope of theinvention is limited only by the claims. Further, unless otherwiserequired by context, singular terms shall include pluralities and pluralterms shall include the singular. Thus, as used herein and in theclaims, the singular forms include the plural reference and vice versaunless the context clearly indicates otherwise.

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients or reaction conditions usedherein should be understood as modified in all instances by the term“about.” The term “about” when used in connection with a value can mean5% of the value being referred to. For example, about 100 means from 95to 105.

As used herein, the term “latex” refers to natural or synthetic latex,which include vulcanized or non-vulcanized. The term “latex polymer”refers to the polymer(s) the latex is formed from. Typically, the latexsubstrate is hydrophobic. In some embodiments, the latex isbiocompatible provided that the user does not have an adverse orallergic reaction when in contact with latex. Synthetic latex mayinclude synthetic rubber materials, including but not limited tonitrile, hydrogenated nitrile, ethylene-propylene, fluorocarbon,chloroprene, silicone, fluorosilicone, polyacrylate, ethylene acrylic,acrylic polymers, styrenebutadiene, acrylonitrile butadiene, polyvinylacetate, or polyurethane rubbers.

As used herein, the term “hydrophilic polymer” refers to homo- orco-polymers that exhibit hydrophilic properties, i.e., having a strongaffinity for water. Non-limiting examples of hydrophilic polymersinclude poly(vinyl pyrrolidone)(PVP), poly(ethylene glycol) (PEG),poly(vinyl alcohol) (PVA), poly(N-isopropylacrylamide), polyacrylamide,poly(2-oxazoline), polyethylenimine, polyacrylic acid),polymethacrylate, poly(2-ethylacrylic acid), poly(acrylic acid),poly(sulfopropyl acrylate) potassium salt, poly(2-methacryloyloxyethylphosphorylchlorine), poly(2-propylacrylic acid), poly(methacrylic acid),poly(2-hydroxypropyl methacrylate), hydroxypropylmethylcellulose (HPMC),poly(oxanorbornene), polyelectrolytes, and co-polymers thereof.

As used herein, the term “hydrophilic latex blend” or “hydrophilic andlatex polymer blend” refers to an evenly-mixed and viscous solutionmixture composed of a hydrophilic polymer and latex dissolved in anaqueous solution.

As used herein, the term “non-cytotoxic” refers to biocompatibility withmammalian cells.

As used herein, the term “biocompatible” refers to the absence of anadverse acute, chronic or escalating biological response to an implantor coating, and is distinguished from a mild, transient inflammationwhich typically accompanies surgery or implantation of foreign objectsinto a living organism.

As used herein, the term “viscous” means a liquid material, e.g., asolution having viscosity of several hundreds centipoises to severalmillions centipoises. For example the measurement of viscosity can rangefrom about 10² cP to about 10⁷ cP.

DETAILED DESCRIPTION OF THE INVENTION

The invention provides a novel hydrophilic polymer and latex polymerblend coating formulation and compositions thereof. These compositionsare suitable for use, for example, as hydrophilic coating on variousdevices, such as condoms and other prophylactic or medical devices, toform hydrophilic and flexible coatings with durable lubricity. When incontact with water or an aqueous solution, the hydrophilic coatingbecomes durably lubricious. This thin hydrophilic coating is able tomaintain its lubricity continuously when in contact with surfaces in thepresence of water without impacting on the mechanical and physicalproperties of the coated device. Thus, frictional forces are loweredwhen in contact with tissue or other interfaces. A durable andlubricious hydrophilic coating on latex condoms can lead to a reductionof condom breakage, pain, discomfort, and mucosal microtrauma for theuser. Other devices that can benefit from such a coating include, forexample, solid, non-flexible and flexible surfaces of prophylactic andbiomedical latex-based devices or tools.

The hydrophilic and latex polymer blend coating formulation includes twomain components in an aqueous environment: a hydrophilic polymer (e.g.,poly(vinyl pyrrolidone)(PVP), poly(ethylene glycol) (PEG), or poly(vinylalcohol) (PVA), and a natural or synthetic latex suspension (e.g.,having a similar composition as the substrate to be coated). These twocomponents are present at a pre-selected ratio and mixed so as togenerate a well-mixed and viscous solution (a liquid suspension). In atypical coating application, for example to a latex condom, a thin andeven layer of the latex blend coating formulation is applied to thesurface of latex condoms (either after a base layer is formed ordirectly on the latex condom) via dip-coating, followed by immediateexposure to heat to evaporate the solvent and form a cured coating.

As is disclosed herein for the first time, the hydrophilic coatings ofthe invention afford: (1) reduced frictional forces at the latex andtissue interfaces, (2) reduced risk of device breakage and infectionsassociated with long-term latex exposure to skin and tissue, (3)improved biocompatibility of latex through imparting a non-foulingsurface, and (4) improved user satisfaction, comfort, and safetyassociated with latex devices.

In one aspect, the invention generally relates to an aqueouscomposition, which comprises: a hydrophilic polymer; a suspension oflatex polymer microparticles; and, optionally, one or more ofvulcanizing or accelerating agents. The hydrophilic polymer has a meanmolecular weight in the range from about 1 kDa to about 10,000 kDa andis present in the composition at a concentration from about 2 w/v % toabout 10 w/v %. The latex polymer microparticles are present in thecomposition at a concentration from about 20 w/v % to about 60 w/v %.The weight ratio of the hydrophilic polymer to the latex polymermicroparticles is in the range from about 1:1 to about 10:1.

Any suitable hydrophilic polymer may be employed. In certainembodiments, the hydrophilic polymer comprises one or more hydrophilicpolymers selected from the group consisting of: homo- or co-polymers ofvinyl pyrrolidone, ethylene glycol, and/or vinyl alcohol. In certainembodiments, the hydrophilic polymer comprises a second hydrophilicpolymer.

In certain embodiments, the hydrophilic polymer comprises one ofpoly(vinyl pyrrolidone)(PVP), poly(ethylene glycol) (PEG), andpoly(vinyl alcohol) (PVA). In certain embodiments, the hydrophilicpolymer comprises PVP.

The hydrophilic polymer may have any suitable molecular weight, forexample, having a mean molecular weight in the range from about 1 kDa toabout 10,000 kDa (e.g., from about 1 kDa to about 5,000 kDa, from about1 kDa to about 1,000 kDa, from about 1 kDa to about 500 kDa, from about1 kDa to about 100 kDa, from about 1 kDa to about 50 kDa, from about 1kDa to about 10 kDa, from about 5 kDa to about 10,000 kDa, from about 10kDa to about 10,000 kDa, from about 50 kDa to about 10,000 kDa, fromabout 100 kDa to about 10,000 kDa, from about 500 kDa to about 10,000kDa, from about 1,000 kDa to about 10,000 kDa, from about 5,000 kDa toabout 10,000 kDa, from about 10 kDa to about 5,000 kDa, from about 50kDa to about 1,000 kDa, from about 100 kDa to about 500 kDa).

In certain embodiments, the hydrophilic polymer has a mean molecularweight in the range from about 1 kDa to about 1,000 kDa (e.g., fromabout 1 kDa to about 50 kDa, from about 50 kDa to about 500 kDa, fromabout 500 kDa to about 1,000 kDa).

In certain embodiments, the hydrophilic polymer has a mean molecularweight in the range from about 1 kDa to about 100 kDa (e.g., from about1 kDa to about 10 kDa, from about 10 kDa to about 50 kDa, from about 50kDa to about 100 kDa).

The hydrophilic polymer may be present in the composition at anysuitable concentration in aqueous composition, for example, from about 2w/v % to about 10 w/v % (e.g., from about 2 w/v % to about 9 w/v %, fromabout 2 w/v % to about 8 w/v %, from about 2 w/v % to about 7 w/v %,from about 2 w/v % to about 6 w/v %, from about 2 w/v % to about 5 w/v%, from about 3 w/v % to about 10 w/v %, from about 4 w/v % to about 10w/v %, from about 5 w/v % to about 10 w/v %, from about 6 w/v % to about10 w/v %, from about 3 w/v % to about 8 w/v %, from about 4 w/v % toabout 9 w/v %,).

In certain embodiments, the hydrophilic polymer is present in thecomposition at a concentration from about 2 w/v % to about 7 w/v %(e.g., from about 2 w/v % to about 3.5 w/v %, from about 3.5 w/v % toabout 5 w/v %, from about 5 w/v % to about 7 w/v %).

The latex polymer microparticles may be natural latex or syntheticlatex. Synthetic rubber latex may be synthesized from, for example,nitrile, butadiene, styrene-butadiene, chloroprene, isobutylene, orco-polymers thereof.

The latex polymer microparticles may be present in the composition atany suitable concentration in aqueous composition, for example, fromabout 20 w/v % to about 65 w/v % (e.g., from about 30 w/v % to about 65w/v %, from about 40 w/v % to about 65 w/v %, from about 50 w/v % toabout 65 w/v %, from about 20 w/v % to about 50 w/v %, from about 20 w/v% to about 40 w/v %, from about 20 w/v % to about 30 w/v %).

In certain embodiments, the latex polymer microparticles is present inthe composition at a concentration from about 35 w/v % to about 55 w/v %(e.g., from about 35 w/v % to about 40 w/v %, from about 40 w/v % toabout 45 w/v %, from about 45 w/v % to about 50 w/v %, from about 50 w/v% to about 55 w/v %).

The weight ratio of the hydrophilic polymer to the latex polymermicroparticles in aqueous composition may be any suitable value, forexample, in the range from about 1:1 to about 1:3 (e.g., about 1:1 toabout 1:2.5, about 1:1 to about 1:2, about 1:1 to about 1:1.5, about1:1.5 to about 1:3, about 1:2 to about 1:3, about 1:2.5 to about 1:3).

The aqueous composition is preferably a well-mixed and stablesuspension.

The aqueous composition is preferably a viscous aqueous composition, forexample, with a viscosity in the range from about 10 cP to about 10¹⁰ cP(e.g., from about 10 cP to about 10² cP, from about 10 cP to about 10⁴cP, from about 10 cP to about 10⁶ cP, from about 10 cP to about 10⁸ cP,from about 10² cP to about 10¹⁰ cP, from about 10⁴ cP to about 10¹⁰ cP,from about 10⁶ cP to about 10¹⁰ cP, from about 10⁸ cP to about 10¹⁰ cP,from about 10² cP to about 10⁶ cP, from about 10⁴ cP to about 10⁸ cP).

The compositions disclosed herein may further include additives thatimpact chemical and/or physical properties of the composition, such asvulcanizing and/or accelerating agents. Any suitable vulcanizing agents(e.g., diisopropyl xanthogen polysulfide, sulfur, or ammonia) may beused. Any suitable accelerating agents (e.g.,zinc-N-diethyl-dithio-carbomate, zinc-N-dibutyl-dithio-carbomate, orammonia) may be used.

The compositions disclosed herein may further include one or more ofantimicrobials, antifungals, antivirals, vitamins, colors, andantibiotics.

In another aspect, the invention generally relates to a compositionformed by mixing: a first aqueous solution of a hydrophilic polymer witha concentration in the range from about 1 w/v % to about 20 w/v %; and asecond aqueous suspension of latex polymer microparticles with aconcentration in the range from about 20 w/v % to about 65 w/v %. Thehydrophilic polymer has a mean molecular weight in the range from about1 kDa to about 1,000 kDa. The volume ratio of the first aqueous solutionto the second aqueous suspension is in the range from about 1:1 to about1:3.

In certain embodiments, the hydrophilic polymer at a concentration inthe composition from about 2 w/v % to about 7 w/v % (e.g., from about 2w/v % to about 3.5 w/v %, from about 3.5 w/v % to about 5 w/v %, fromabout 5 w/v % to about 7 w/v %) and the latex polymer microparticles ata concentration from about 20 w/v % to about 65 w/v % (e.g., e.g., fromabout 30 w/v % to about 65 w/v %, from about 40 w/v % to about 65 w/v %,from about 50 w/v % to about 65 w/v %, from about 20 w/v % to about 50w/v %, from about 20 w/v % to about 40 w/v %, from about 20 w/v % toabout 30 w/v %).

In certain embodiments, the composition includes one or more ofvulcanizing agents. In certain embodiments, the composition includes oneor more of accelerating agents.

In certain embodiments, one or more of vulcanizing agents or the one ormore of accelerating agents are present in the first aqueous solution ahydrophilic polymer.

In certain embodiments, one or more of vulcanizing agents or the one ormore of accelerating agents are present in the second aqueous suspensionof latex polymer microparticles.

In certain embodiments, the vulcanizing agents are selected from thegroup consisting of: diisopropyl xanthogen polysulfide, sulfur andammonia.

In certain embodiments, the accelerating agents are selected from thegroup consisting of: zinc-N-diethyl-dithio-carbomate,zinc-N-dibutyl-dithio-carbomate and ammonia.

In certain embodiments, one or more of antimicrobials, antifungals,antivirals, vitamins, colors, or antibiotics may be present in the firstaqueous solution a hydrophilic polymer.

In certain embodiments, one or more of antimicrobials, antifungals,antivirals, vitamins, colors, or antibiotics may be present in thesecond aqueous suspension of latex polymer microparticles.

In yet another aspect, the invention generally relates to a curedmaterial formed by heating a composition disclosed herein for a timesufficient to form interpenetrating polymer networks of crosslinkedhydrophilic polymer and latex polymer.

In certain embodiments, the material is a coating forming a surface of aproduct. In certain embodiments, the material is a coating forming apartial surface of a product. In certain embodiments, the material is acoating forming a complete surface of a product.

The cured material may be used with any suitable product, for example,selected from the group consisting: a condom, a sex toy, a surgicaldevice, a medical implant, or a glove.

In certain embodiments, the cured material is less toxic than theuncured coated material.

In yet another aspect, the invention generally relates to a latexcondom. The latex condom includes: a sheath of an elastomeric materialselected from natural or synthetic rubber latex, the sheath having anouter surface and an inner surface; and a layered coating comprising afirst or base layer disposed on and adhered to at least a portion of theouter surface of the sheath and a second or top layer disposed on andadhered to at least a portion of the first or base layer. The first orbase layer is a cured latex polymer. The second or top layer is a curedblend of a latex polymer and a hydrophilic polymer having a meanmolecular weight in the range from about 1 kDa to about 1,000 Da,wherein the weight ratio of the hydrophilic polymer to the latex polymeris in the range from about 10:1 to about 1:10.

In certain embodiments, the layered coating includes a third or toplayer disposed on and adhered to the second layer, wherein the third ortop layer is a cured blend of latex polymer and a hydrophilic polymerhaving a mean molecular weight in the range from about 1 kDa to about1,000 kDa, wherein the weight ratio of the hydrophilic polymer to thelatex polymer is in the range from about 1:1 to about 10:1.

In certain embodiments, the layered coating comprising a further or toplayer disposed on and adhered to the third layer, wherein the further ortop layer is a cured blend of latex polymer and a hydrophilic polymerhaving a mean molecular weight in the range from about 1 kDa to about1,000 kDa, wherein the weight ratio of the hydrophilic polymer to thelatex polymer is in the range from about 1:1 to about 10:1.

In certain embodiments, the first layer covers substantially the entireouter surface of the latex condom, the second layer covers substantiallyall of the first layer, and, if present, the third layer coverssubstantially all of the second layer surface, and so forth,respectively.

In certain embodiments, the elastomeric material is selected fromnatural or synthetic rubber latex. In certain embodiments, the syntheticrubber latex is synthetized from nitrile, butadiene, styrene-butadiene,chloroprene, isobutylene, or co-polymers thereof.

In certain embodiments, the weight ratio of the hydrophilic polymer tothe latex polymer is in the range from about 1:1 to about 10:1 (e.g.,from about 1:1 to about 7:1, from about 1:1 to about 5:1, from about 1:1to about 3:1, from about 3:1 to about 10:1, from about 5:1 to about10:1, from about 7:1 to about 10:1).

In certain embodiments, the weight ratio of the hydrophilic polymer tothe latex polymer is in the range from about 1:1 to about 5:1 (e.g.,from about 1:1 to about 3:1, from about 1:1 to about 3:1, from about 5:1to about 5:1, from about 3:1 to about 5:1).

In certain embodiments, the hydrophilic polymer comprises one ofpoly(vinyl pyrrolidone)(PVP), poly(ethylene glycol) (PEG), andpoly(vinyl alcohol) (PVA). In certain embodiments, the hydrophilicpolymer comprises PVP.

In certain embodiments, the hydrophilic polymer comprises a secondhydrophilic polymer.

In certain embodiments, the latex condom further includes asilicon-based or water-based lubricant applied to the top layer.

In certain embodiments, the latex condom further includes a coating ofpowders or dusting agents, selected from cornstarch, baby powder, ortalc, applied to the top layer.

In certain embodiments, when the latex condom contacts with moisture orwater, the top layer becomes slippery with durable lubricity.

In yet another aspect, the invention generally relates to a packagedcondom product comprising one or more latex condoms disclosed herein.

In yet another aspect, the invention generally relates to a method formanufacturing a condom. The method includes: providing a sheath of anelastomeric material selected from natural or synthetic rubber latex,the sheath having an outer surface and an inner surface; depositing afirst layer of an aqueous suspension of a latex polymer to at least aportion of the outer surface of the sheath; curing the latex polymerwith exposure to heat for a time sufficient to form a first or baselayer of cured latex polymer; depositing a second layer of acomposition, comprising a hydrophilic polymer and a suspension of latexpolymer, to at least a portion of the first or base layer; and curingthe second layer of hydrophilic polymer and latex polymer with exposureto heat for a time sufficient to form a second or top layer. Thehydrophilic polymer has a mean molecular weight in the range from about1 kDa to about 1,000 kDa and is present in the composition at aconcentration from about 2 w/v % to about 10 w/v %. The latex polymermicroparticles are present in the composition at a concentration fromabout 20 w/v % to about 65 w/v %. The weight ratio of the hydrophilicpolymer to the latex polymer microparticles is in the range from about1:1 to about 10:1.

In certain embodiments, the method further includes: depositing a thirdor top layer of a composition, comprising a hydrophilic polymer and asuspension of latex polymer, to at least a portion of the second layer;and curing the third layer of hydrophilic polymer and latex polymer withexposure to heat for a time sufficient to form a third or top layer.

In certain embodiments, the first layer covers substantially all of theouter surface of the latex condom, the second layer covers substantiallyall of the first layer, and, if present, the third layer coverssubstantially all of the second layer surface, and so forth,respectively.

In certain embodiments, curing the latex polymer is conducted at atemperature between about 25° C. to about 70° C. (e.g., between about35° C. to about 70° C., about 40° C. to about 70° C., about 50° C. toabout 70° C., about 60° C. to about 70° C., about 25° C. to about 60°C., about 25° C. to about 50° C., about 25° C. to about 40° C., about30° C. to about 60° C.) for a time period from about 5 to about 60minutes (e.g., from about 5 to about 45 minutes, from about 5 to about30 minutes, from about 5 to about 15 minutes, from about 5 to about 10minutes, from about 10 to about 30 minutes, from about 15 to about 30minutes, from about 20 to about 30 minutes, from about 10 to about 25minutes, from about 10 to about 20 minutes).

In certain embodiments, curing the hydrophilic polymer and a suspensionof latex polymer is conducted at a temperature between about 25° C. toabout 70° C. (e.g., between about 35° C. to about 70° C., about 40° C.to about 70° C., about 50° C. to about 70° C., about 60° C. to about 70°C., about 25° C. to about 60° C., about 25° C. to about 50° C., about25° C. to about 40° C., about 30° C. to about 60° C.) for a time periodfrom about 5 to about 60 minutes (e.g., from about 5 to about 45minutes, from about 5 to about 30 minutes, from about 5 to about 15minutes, from about 5 to about 10 minutes, from about 10 to about 30minutes, from about 15 to about 30 minutes, from about 20 to about 30minutes, from about 10 to about 25 minutes, from about 10 to about 20minutes).

In certain embodiments, subsequent coating layers (e.g., second or thirdlayers) are applied to the base layer immediately following curing whilethe base layer is still at elevated temperature (i.e., above 25° C.). Inother embodiments, the base layer fully cools to room temperature (i.e.,25° C.) prior to application of subsequent coating layers.

In certain embodiments, the first or base layer has a thickness in therange from about 0.01 mm to about 1.0 mm (e.g., from about 0.02 mm toabout 1.0 mm, from about 0.05 mm to about 1.0 mm, from about 0.1 mm toabout 1.0 mm, from about 0.2 mm to about 1.0 mm, from about 0.4 mm toabout 1.0 mm, from about 0.6 mm to about 1.0 mm, from about 0.01 mm toabout 0.8 mm, from about 0.01 mm to about 0.5 mm, from about 0.01 mm toabout 0.2 mm, from about 0.01 mm to about 0.1 mm, from about 0.01 mm toabout 0.08 mm, from about 0.01 mm to about 0.05 mm, from about 0.05 mmto about 0.1 mm).

In certain embodiments, the first or base layer has a thickness lessthan about 1.0 mm (e.g., less than about 0.8 mm, less than about 0.5 mm,less than about 0.4 mm, less than about 0.2 mm, less than about 0.1 mm,less than about 0.05 mm).

In certain embodiments, the second, or the third if present, or toplayer has a thickness in the range from about 0.01 mm to about 1.0 mm(e.g., from about 0.02 mm to about 1.0 mm, from about 0.05 mm to about1.0 mm, from about 0.1 mm to about 1.0 mm, from about 0.2 mm to about1.0 mm, from about 0.4 mm to about 1.0 mm, from about 0.6 mm to about1.0 mm, from about 0.01 mm to about 0.8 mm, from about 0.01 mm to about0.5 mm, from about 0.01 mm to about 0.2 mm, from about 0.01 mm to about0.1 mm, from about 0.01 mm to about 0.08 mm, from about 0.01 mm to about0.05 mm, from about 0.05 mm to about 0.1 mm).

In certain embodiments, the second, or the third if present, or toplayer has a thickness less than about 1.0 mm (e.g., less than about 0.8mm, less than about 0.5 mm, less than about 0.4 mm, less than about 0.2mm, less than about 0.1 mm, less than about 0.05 mm).

As discussed herein, in certain preferred embodiments, the coatingapplication consists of applying a layer of the hydrophilic and latexpolymer blend coating formulation over a latex base layer, which isapplied to the latex product surface. In some embodiments, thesequential hydrophilic coating application and curing process may berepeated a plurality of times. For example, a hydrophilic and latexpolymer coating is applied onto a latex substrate with a subsequentlayer being the hydrophilic and latex polymer latex. In anotherembodiment, the subsequent hydrophilic and latex polymer is applied ontoa hydrophilic and latex polymer coating blend that served as the firstor base layer. In some embodiments, multiple coatings can be applieddependent on the desired properties to be achieved. Exemplary coatingstrategies are listed in Table 1.

TABLE 1 Coating layer order in various coating process embodimentsCoating Layer 1 Coating Layer 2 Coating Layer 3 A Latex Hydrophilic andLatex Polymer blend coating formulation B Hydrophilic and Latex LatexPolymer coating formulation C Latex Hydrophilic and Hydrophilic andLatex Polymer Latex Polymer coating formulation coating formulation DHydrophilic and Hydrophilic and Latex Latex Polymer Latex Polymercoating formulation coating formulation E Latex Latex Hydrophilic andLatex Polymer coating formulation F Hydrophilic and Latex Latex LatexPolymer coating formulation G Hydrophilic and Latex Hydrophilic andLatex Polymer Latex Polymer coating formulation coating formulation HLatex Hydrophilic and Latex Latex Polymer coating formulation

In yet another aspect, the invention generally relates to a condommanufactured by a method disclosed herein.

As disclosed herein, suitable additives may be added to assist inachieving one or more desired properties or enhancements in thecompositions or products of the inventions.

In certain embodiments, the hydrophilic and latex polymer blend coatingformulation, and the coated product, includes one or more antimicrobialssuch as antifungals, antibacterials, and metallic nanoparticles and/ormicroparticles that deter microbial growth. Examples of antifungalagents include, but are not limited to, Amphotericin B, lactic acid,sorbic acid, Clotrimazole, Ciclopirox, Carbol-Fushsin Econazole,Enilconazole, Fluconazole, Griseofulvin, Halogropin, Introconazole,Ketoconazole, Miconazole, Mafenide, Naftifine, Nystatin, Oxiconazole,Thiabendazole, Sulconazole, Tolnaftate, Undecylenic acid, Terbinafine,and Silver Sulfadiazine. Additionally, antibiotics and otherantimicrobial agents can be selected from the group consisting ofbacitracin; the cephalosporins (such as cefazolin, cefadroxil,cephalothin, cephalexin, ceftazidime, ceftriaxone, ceftizoxime, andmeropenem); cycloserine; fosfomycin, the penicillins (such asamdinocillin, amoxicillin, ampicillin, azlocillin, benzathine penicillinG, bacamipicillin, carbenicillin, cyclacillin, cloxacillin,dicloxacillin, mezlocillin, methicillin, oxacillin, nafcillin,penicillin G, penicillin V, piperacillin, and ticarcillin); vancomycin;ristocetin; colistin; novobiocin; the polymyxins (such as colistin,colistimathate, and polymyxin B); the aminoglycosides (such as neomycin,amikacin, kanamycin, gentamicin, netilmicin, paromomycin, streptomycin,spectinomycin, and tobramycin), the tetracyclines (such asdemeclocycline, do+-xycycline, minocycline, methacycline, andoxytetracycline); carbapenems (such as imipenem); monobactams (such asaztreonam); clindamycin; chloramphenicol; cycloheximide; fucidin;lincomycin; rifampicin; puromycin; other streptomycins; the macrolides(such as erythromycin and oleandomycin); the fluoroquinolones;actinomycin; ethambutol; 5-fluorocytosine; griseofulvin; rifamycins; thesulfonamides (such as sulfacytine, sulfadiazine, sulfisoxazole,sulfamethoxazole, sulfamethizole, and sulfapyridine); and trimethoprim.Other antibacterial agents include, but are not limited to, bismuthcontaining compounds (such as bismuth aluminate, bismuth subcitrate,bismuth subgalate, and bismuth subsalicylate); nitrofurans (such asnitrofurazone, nitrofurantoin, and furozolidone); metronidazole;tinidazole; nimorazole; zinc-, copper-, or silver-based compounds,particles (micro- or nano-) and benzoic acid.

In certain embodiments, the hydrophilic and latex polymer blend coatingformulation, and the coated product, includes one or more antivirals,antiretrovirals, or any like compounds that prevent the spread ofviruses. Examples of antiviral agents can include, but are not limitedto, adamantine antivirals, antiviral boosters, antiviral combinations,antiviral interferons, chemokine receptor antagonist, integrase strandtransfer inhibitor, miscellaneous antivirals, neuraminidase inhibitors,NNRTIs, NS5A inhibitors, nucleoside reverse transcriptase inhibitors,protease inhibitors, and purine nucleosides. Other agents and drugs canalso include Abacavir, Aciclovir, Acyclovir, Adefovir, Amantadine,Amprenavir, Ampligen, Arbidol, Atazanavir, Atripla, Balavir, Cidofovir,Combivir, Dolutegravir, Darunavir, Delavirdine, Didanosine, Docosanol,Edoxudine, Efavirenz, Emtricitabine, Enfuvirtide, Entecavir, Ecoliever,Famciclovir, Fomivirsen, Fosamprenavir, Foscarnet, Fosfonet, Fusioninhibitor, Ganciclovir, Ibacitabine, Imunovir, Idoxuridine, Imiquimod,Indinavir, Inosine, Integrase inhibitor, Interferon type III, Interferontype II, Interferon type I, Interferon, Lamivudine, Lopinavir, Loviride,Maraviroc, Moroxydine, Methisazone, Nelfinavir, Nevirapine, Nexavir,Nitazoxanide, Nucleoside analogues, Novir, Oseltamivir (Tamiflu),Peginterferon alfa-2a, Penciclovir, Peramivir, Pleconaril,Podophyllotoxin, Protease inhibitor (pharmacology), Raltegravir, Reversetranscriptase inhibitor, Ribavirin, Rimantadine, Ritonavir, Pyramidine,Saquinavir, Sofosbuvir, Stavudine, Synergistic enhancer(antiretroviral), Telaprevir, Tenofovir, Tenofovir disoproxil,Tipranavir, Trifluridine, Trizivir, Tromantadine, Truvada, Valaciclovir(Valtrex), Valganciclovir, Vicriviroc, Vidarabine, Viramidine,Zalcitabine, Zanamivir (Relenza), and Zidovudine.

In certain embodiments, the hydrophilic and latex polymer blend coatingformulation, and the coated product, includes one or more vitamins, forexample, Vitamins A, C, D, E, K and B, as well as thiamine (B1),riboflavin (B2), niacin (B3), pantothenic acid (B5), pyroxidine(B6),biotin (B7), folate (B9) and cobalamin (B12).

In certain embodiments, the hydrophilic and latex polymer blend coatingformulation, and the coated product, includes one or more pigments orcolorants, for example, C.I. Pigment Red 48:2 Permanent Carmine, C.I.Pigment Blue 15:2/Copper Phthalocyanine Blue, C.I. Pigment Green7/Polychloro Copper phthalocyanine Green, C.I. Pigment Yellow 74 AzoYellow.

In certain embodiments, the hydrophilic and latex polymer blend coatingformulation, and the coated product, include other additives suitablefor use with a condom product, such as one or more of plasticizers,accelerators, stabilizers, anticoagulants, preservatives, or othercompounds can be added to the natural or synthetic latex solution toassist or accelerate the vulcanization process or to improve itsmechanical properties. In some embodiments, these additives can include,but are not limited to, ammonia, proteins, nitrosamine, zinc chloride,zinc oxide, stearic acid, antidegradants, plasticizers, sulfur,peroxides, acetic acid, citric acid, formic acid, metallic oxides,potassium laurate, acetoxysilanes, urethane crosslinkers,polychloroprene, ethylene thiourea, or other equivalent accelerators,catalysis, or curatives. In another embodiment, more than one of theseadditives or compounds can be added into the latex solution.

The following examples are meant to be illustrative of the practice ofthe invention, and not limiting in any way.

EXAMPLES Hydrophilic and Latex Polymer Blend Formulations and CoatedCondoms

The hydrophilic and latex polymer blend formulation was studied byexploring different (1) hydrophilic polymer concentrations in water(e.g., ranging from 20 w/v % to 0.5 w/y %; (2) hydrophilic polymers(e.g., PEG, PVP, and PVA); (3) latex polymer solid content concentrationin solution (e g from 40-60 w/v %); (4) solution ratios to blend thedissolved hydrophilic polymer in water and latex polymer suspension toproduce the hydrophilic and latex polymer blend; and (5) viscosities ofthe hydrophilic and latex polymer blend and their effects on thehomogeneity and thickness of the condom coating application.

Well-mixed solutions were used with the two components evenlydistributed throughout the solution. Various formulations were used tocoat latex substrates on glass slides (applied with heat at 60° C. toeliminate ITV exposure) and were inspected to meet the followingrequirements: (1) have a slippery coated surface touch after rubbingsamples back-and-forth 20 times with fingers and water; (2) maintain theelasticity and flexibility of natural rubber when stretched on aninstron without breaking; and (3) hydrophilic and latex polymer blendcoating did not delaminate, peel, or crack after rubbing and stretching.

Certain preferred hydrophilic and latex polymer blend formulations wereidentified to have an about 5% w/v polyvinylpyrrolidone (PVP) dissolvedin water that was blended with an about 40 w/v % latex solution. Thewell-mixed hydrophilic and latex polymer blend coating formulation wasreproducibly applied onto latex condoms using a dip-coating approach andis cured onto latex surfaces using heat at about 60° C. for about 15minutes. This prototype resulted in a coating that was thin andflexible, possessed similar mechanical and physical properties as thelatex, and had good adhesion properties onto latex substrates (e.g., nocracking, delamination, peeling).

TABLE 2 Latex blend coating formulations preparation with PEG, PVP, andPVA Hydrophilic Stock Solution Hydrophilic and Latex Blend Ratio polymer(w/v %) (liquid latex:hydrophilic polymer) PEG 20 1:1 2:1 1:2 5:1 1:5 101:1 2:1 1:2 5:1 1:5 5 1:1 2:1 1:2 5:1 1:5 1 1:1 2:1 1:2 5:1 1:5 PVP 201:1 2:1 1:2 5:1 1:5 10 1:1 2:1 1:2 5:1 1:5 5 1:1 2:1 1:2 5:1 1:5 1 1:12:1 1:2 5:1 1:5 PVA 20 1:1 2:1 1:2 5:1 1:5 10 1:1 2:1 1:2 5:1 1:5 5 1:12:1 1:2 5:1 1:5 1 1:1 2:1 1:2 5:1 1:5

Non-lubricated latex condoms were unrolled, washed with water, andpatted dry to remove any starchy powder from the packaging. Latex condomstrips (2×6 cm) were cut from the latex condoms and mounted on glassslides. 5 mL of latex blend coating formulations were prepared by mixingfreshly purchased liquid latex (natural rubber) with stock solutions ofpolyvinyl pyrrolidone (PVP), poly(ethylene glycol) (PEG), or polyvinylalcohol) (PVA) in water. According to Table 2, each of the hydrophilicand latex polymer blend coating formulations were prepared by firstdissolving the hydrophilic polymer in water at varying water to stocksolution ratios, as measured in total weight to stock solution volume.This solution was then mixed with the latex suspension at varyinglatex-to-hydrophilic polymer solution ratios as noted in Table 2. A thineven layer of each solution was placed onto the latex strips which wereimmediately placed in an oven at about 60° C. to be dried for about 15minutes. Samples were removed from the oven and allowed to cool to roomtemperature before assessing the coating.

Each of the hydrophilic and latex polymer blend coating formulation andrespective coated latex samples were evaluated via touch with andwithout water by contact with dry skin and assessed according to thefollowing parameters: (A) feasibility to obtain a well-mixed, viscoussolution when mixed; (B) ability to maintain similar flexible propertiesas non-lubricated, uncoated latex condoms when stretched without water;(C) slippery and lubricous when wetted; and, finally (D) ability tomaintain lubricity after about 20 rubs when wetted.

The degree of slipperiness and lubricity in parameter (C) was furtherevaluated subjectively in comparison to uncoated latex condom stripswith the following ratings: (1) similar to plain latex, (2) slippery,and (3) very slippery.

Tables 3-5 summarize the assessments of the latex blend coatingformulations and their resulting coatings on latex strips when preparedwith PEG, PVP, and PVA, respectively. In view of the results presentedin Table 3 for PEG formulations, none of the PEG formulations showedimproved slipperiness, parameter (C), as compared to a conventionaluncoated condom.

In view of the results presented in Table 4 for PVP formulations, thePVP formulations in the range of about 10.0 to about 12.5 w/v % withratios of about 1:1, 2:1 and 1:2 as well as a PVP formulation of about5.0 w/v % with a ratio about 1:1 are each demonstrated to have (A)feasibility to obtain a well-mixed, viscous solution when mixed; (B)ability to maintain similar flexible properties as non-lubricated,uncoated latex condoms when stretched without water; (C) very slipperyor slippery and lubricous when wetted as compared to a conventionaluncoated condom as according to the following rating system: (1) similarto plain latex; (2) slippery; and (3) very slippery; and, (D) ability tomaintain lubricity after about 20 rubs when wetted.

In view of Table 5 for PVA formulations, the PVA formulation of about5.0 w/y % with a ratio of about 1:5 is demonstrated to have (A)feasibility to obtain a well-mixed, viscous solution when mixed; (B)ability to maintain similar flexible properties as non-lubricated;uncoated latex condoms when stretched without water; (C) very slipperyor slippery and lubricous when wetted as compared to a conventionaluncoated condom; and, (D) ability to maintain lubricity after about 20rubs when wetted.

Accordingly in view of Tables 3-5, that the preferred coating resultedfrom a hydrophilic and latex polymer blend coating formulation preparedwith about 10 w/v % to about 12 w/v % PVP in water mixed with a liquidlatex solution at about 1:1 or 1:2 ratio. A preferred hydrophilic andlatex polymer blend formulation has a final PVP concentration of about 2w/y % to about 8 w/y % as noted in Table 5.

Identifying the appropriate hydrophilic polymer, as well as optimizingthe concentration ranges and method for formulation preparation todevelop the final solution was critical to develop a robust, flexible,and elastic cured substrate coating that possessed long-lastinglubricating surface with water. PVP was particularity selected sinceboth PEG and PVA did not offer the desired lubricating properties on thelatex surface even at high concentrations up to 20 w/y % as theirslippery properties did not consistently last up till 20 rubs usingfingers in the presence of water. PVA polymers are known to be rigidwhich in return reduces the flexibility of the latex substrate, thusinhibiting its ability to be stretched and elastic. When varying ratiosof PVP in water was mixed with the liquid latex suspension, lowconcentrations of PVP in the final solution (e.g. <2 w/v %) resulted inlimited durability of the coating's lubricating properties due toinsufficient PVP present in the final cured substrate. Yet, with higherconcentrations of PVP (e.g. >8 w/v %) in the final concentrationsolution in relation to liquid latex, this interfered with the abilityfor latex to cure to form a durable flexible substrate while inhibitingthe formation an interpenetrating network with the PVP. As a result, thecured substrates were brittle and easily broke when bent and stretched.Similar observations were also noted with solutions containing lowconcentrations of latex in solution (e.g. >20 w/v %). Higherconcentrations of latex in the final formulation (e.g. >30 w/v %) alsoinhibit the lubricating properties of PVP in solution due to the largeconcentration and presence of latex in the solution, which masked thePVP within the interpenetrating network.

TABLE 3 Assessment of latex blend coating formulations and resultingcoating with PEG Assessment Parameters Latex Blend of Coating on LatexStrips Formulation C with PEG A B 1 2 3 D 20 w/v % 1:1 X X X 2:1 X X X1:2 X X 5:1 X X X 1:5 X X 10 w/v % 1:1 X X X 2:1 X X X 1:2 X X 5:1 X X X1:5 X X  5 w/v % 1:1 X X X 2:1 X X X 1:2 X X 5:1 X X X 1:5 X X  1 w/v %1:1 X X 2:1 X X 1:2 X X 5:1 X X X 1:5 X X

TABLE 4 Assessment of hydrophilic and latex polymer blend coatingformulations and resulting coating with PVP Assessment Parameters ofLatex Blend Coating on Latex Strips Formulation C with PVP A B 1 2 3 D20 w/v % 1:1 X X 2:1 X X 1:2 X X 5:1 X X X 1:5 X X 15 w/v % 1:1 X X 2:1X X 1:2 X X 3:1 X X 1:3 X X 12.5 w/v %   1:1 X X X X 2:1 X X X X 1:2 X XX X 3:1 X X X 1:3 X X X 10 w/v % 1:1 X X X X 2:1 X X X X 1:2 X X X X 3:1X X 1:3 X X 5:1 X X X 1:5 X X 7.5 w/v %  1:1 X X X 2:1 X X X 1:2 X X X3:1 X X X 1:3 X X X  5 w/v % 1:1 X X X X 2:1 X X X 1:2 X X X 3:1 X X X1:3 X X X 5:1 X X X 1:5 X X  1 w/v % 1:1 X X X 2:1 X X X 1:2 X X X 5:1 XX X 1:5 X X

TABLE 5 Assessment of hydrophilic and latex polymer blend coatingformulations and resulting coating with PVA Assessment Parameters ofLatex Blend Coating on Latex Strips Formulation with C PVA A B 1 2 3 D20 w/v % 1:1 X 2:1 X 1:2 X 5:1 X X X 1:5 X X 10 w/v % 1:1 X X 2:1 X X1:2 X X 5:1 X X 1:5 X X X  5 w/v % 1:1 X X X X 2:1 X X X X 1:2 X X X X5:1 X X X X 1:5 X X X X  1 w/v % 1:1 X X X X 2:1 X X X X 1:2 X X X X 5:1X X X X 1:5 X X X X

The physical and lubrication properties of the hydrophilic and latexpolymer blend-coated condoms were analyzed in accordance to parameterslisted in Table 6. The results revealed that (1) the hydrophilic andlatex polymer blend formulation was reproducibly scalable (e.g., on aliter and multi-kilo-liter scale) with a quicker dip-coating applicationonto latex substrates, (2) hydrophilic and latex polymer blend coatingresulted in improved adhesion with heat (no peeling, cracking, ordelamination noted when stretched) to the latex without damaging thematerial (tensile testing), (3) hydrophilic and latex polymer blendcoating had improved mechanical properties and flexibility whenstretched with(out) water, (4) the hydrophilic and latex polymerblend-coated condoms had long-lasting lubrication durability in thepresence of water through friction studies with a male masturbator. Thehydrophilic and latex polymer blend coating was slippery with water andaqueous solutions via touch, thin and homogenous (measured with adigital micrometer/SEM and AFM studies), non-cytotoxic, and flexible.The hydrophilic and latex polymer blend-coated condoms also maintainedconsistently lower frictional forces compared to commercial lubricantsand standard lubricated condoms.

TABLE 6 Tested parameters for hydrophilic and latex polymer blend-coatedcondoms Test/Analysis Parameters Coating Thickness 1.0-0.6 mm of HGCoaton latex Visual inspection Presence of a homogenous surface/coatingapplica- tion reproducibility between units and batches CoatingDurability Coating remains on surface after rubbing with Studies #1fingers after 10 times with water Coating Durability Coating presentafter 20 insertions into masturbator Studies #2 Airburst testing N = 3;must hold 18 L of air at 1 kPa/conducted under ISO standards

Coating Process for Large-Scale GMP Manufacturing of Hydrophilic andLatex Polymer Blend-Coated Condoms

The followings were studied: (1) the large scale production of thehydrophilic and latex polymer blend formulation (e.g., on a multi-literscale), (2) adaptation of dip-coating processes and equipment forcoating application under GMP standards, (3) automation of thedip-coating application process onto latex condoms, (4) variousdip-coating speed ranges and their effects on the coating thickness andapplication homogeneity, and (5) reproducibility and uniformity of thecoating application on condoms through different units and batches atvarying speed.

The formulation prototype prepared on a 500 ml, scale for laboratoryassessments and on a 2 to 3 L scale under GMP standards werereproducible and consistent between 3 different batches. FIG. 2 depictsminor adjustments made to the dip-coating instrumentation to translatemanual dipping the hydrophilic and latex polymer blend coatingapplication procedure (FIG. 1C) to an automatic process. The hydrophilicand latex polymer blend-coated condoms prepared with this setup wereconsistent between the units and batches. In conclusion, these resultsdemonstrated the feasibly for the hydrophilic and latex polymer blendformulation to be scalable in the large-scale manufacturing.

The preferred dip-coating speed range was identified for forming thefirst base layer and the second hydrophilic and latex polymer blendlayer to generate a homogenous and thin coating. Small batches of thehydrophilic and latex polymer blend-coated condoms, ranging from 2-26units per batch, were produced and analyzed based on parameters in Table6.

As demonstrated in FIG. 1C, an 1$ mm glass mandrel was placed into thelatex solution to form the first base coat layer using dip-coatingspeeds ranging from about 0.1 mL/min to about 0.4 mL/min. Once removedfrom the barrel, the glass mandrel was held over the solution to allowexcess material to drip off for about 5 seconds while observing an evenlayer of latex solution on the mandrel. If an uneven layer was noted,the dip was repeated. The sample was cured in an oven at about 60° C.for about 10 minutes and then immediately dipped into a second barrelwith the hydrophilic and latex polymer blend formulation at dip-coatingspeeds from about 0.2 mL/min to about 1.0 mL/min. Similarly, once theglass mandrel was removed, excess material dripped off for 5 secondswhile examining an even coating on the latex surface. After heat curingthe sample at about 60° C. for about 15 minutes, the sample cooled toroom temperature, covered in alumni foil, and packaged in an airtightbag for further assessment. Details regarding the number of trial runsand dip-coating speed rates investigated are summarized in Table 7.

TABLE 7 Results of Trial Batches with Varying Dipping Speeds DippingVisual Inspection Slippery Speeds Even w/ water Thickness No. of(mL/min) Uniformity coating by touch Measurements^(*,□)(mm) Batch CondomBase Top between on each and Durability Airburst Near run Units CoatCoat batches unit rubbing Studies^(w) Testing* Opening Middle Near Tip 16 0.1 0.2 Yes Yes Yes Yes Pass 1.01 1.03 1.21 2 12 0.1 0.2 Yes Yes YesYes Fail 0.47 0.52 1.02 3 26 0.1 0.2 Yes Yes Yes Yes Fail 1.05 0.84 0.784 12 0.2 0.2 Yes Yes Yes Yes Fail 0.41 0.54 0.98 5 6 0.2 0.4 Yes Yes YesYes Fail 0.56 0.72 1.34 6 12 0.2 0.4 Yes Yes Yes Yes Fail 0.70 0.57 0.697 12 0.3 0.6 Yes Yes Yes Yes Pass 0.60 1.03 0.60 8 6 0.4 1.0 Yes Yes YesYes Pass 0.60 0.68 1.04 9 12 0.4 1.0 Yes Yes Yes Yes Pass 0.80 0.56 1.04*Studies were done in accordance to requirements and standards statedunder ISO 4074 Studies were conducted at n = 3 that were randomlyselected in the batch produced; measurements shown are averages^(W)coating present after 20 insertions into masturbator with water

A visual inspection of all samples was performed for uniformity betweenunits and batches to ensure an even homogenous coating on the surface.Samples were wetted with water and rubbed with fingers to validate thelubricating properties of the coating. The coating durability was alsotested by inserting 3 randomly selected samples per batch into the malemasturbator 20 times with about 1.0 mL of water to ensure the coatingremained present on the surface.

Thickness measurements using a digital micrometer on 3 selected unitsper batch (i.e. body, reservoir tip, base) were performed in accordanceto ISO 4074. Three samples were sent to Akron Rubber DevelopmentLaboratory (Akron, Ohio) for airburst testing to ensure condoms couldhold a minimum of 18 L of air at 1 kPa as stated under the ISOrequirements. The results are summarized in Table 7.

The studies indicated that a preferred dip-coating speeds of about 0.3mL/min to about 0.4 mL/ruin for the base layer and about 0.6 mL/min toabout 1.0 mL/min for the second or top coat. The hydrophilic and latexpolymer blend-coated condoms prepared at these speed ranges have met theparameters in Table 7 and were used for the following characterizationstudies.

Through frictional studies using a male masturbator, the hydrophilic andlatex polymer blend-coated condoms showed improved durability andlonger-lasting lubrication properties when compared to commerciallyavailable lubricants and personal lubrication products. Cytotoxicity ofthe hydrophilic and latex polymer blend-coated condoms were assessedusing an epithetical fibroblast cell line in accordance to ISO 10993,which showed coated latex samples to have minimized cytotoxicitycompared to non-coated latex samples.

Mechanical testing of the hydrophilic and latex polymer blend-coatedcondoms were performed at Akron Rubber Development Laboratory (Akron,Ohio) in accordance to ISO 4074, To test for holes, water leak testswere conducted by filling the hydrophilic and latex polymer blend-coatedcondoms with 300 mL of water, tying the opening, and manuallyhand-rolling condoms on color absorbent paper with slight pressure.Airburst testing was performed by filling condoms with a minimum of 18L. of air at 1 kPa (FIG. 3). Dimensional analyses were conducted bymeasuring the length of the condom using a ruler while the thickness ofthe condom using a standard digital micrometer near the opening, middle,and tip of the condom (FIG. 3). To ensure the coating did not weaken thelatex, tensile testing was conducted with strips sectioned from thecondom and were stretched at a rate of 500 mm/min. Commerciallyavailable lubricated condoms were included in the studies as controls.

The hydrophilic and latex polymer blend-coated condoms prepared usingdip-coating speeds of about 0.3 mL/min to about 0.4 mL/min (base layer)and about 0.6 mL/min to about 1.0 mL/min (second or top coat) metrequirements under ISO airburst and water-leak testing (Table 7).Tensile testing of the hydrophilic and latex polymer blend-coatedcondoms revealed similar results compared Trojan, Durex, and Lifestylesstandard lubricated condoms, indicating that the hydrophilic and latexpolymer blend coating did not weaken the latex material. Dimensionalanalysis data indicated condoms to be comparable in length and thicknessto commercially available condoms (FIG. 3).

To achieve uniform thickness for the hydrophilic and latex polymer blendcoating condoms in GMP manufacturing, glass mandrels can besimultaneously dipped and rotated into the glass barrel which areimmediately removed and flipped to create a homogenous and even layer ofthe latex solutions on the glass mandrels.

Lubricity of the Hydrophilic and Latex Polymer Blend-Coated Condoms

Studies were performed regarding the minimal amount of water needed tolubricate the hydrophilic and latex polymer blend-coated condom surface,as well as the effects of water-based lubricants (KY liquid). For afully unrolled hydrophilic and latex polymer blend-coated condom(standard 16 mm in length; 4 mm in diameter), it was determined that aminimum amount of 0.50 nit of water was needed to lubricate the entirecoated condom surface. Lower amounts of water 0.25 mL) only partiallywetted the condom surface whereas >0.50 mL of water (e.g., 0.75 mL and1.0 mL) did not attribute any additional lubricating properties orenhanced the coating slipperiness. Studies were repeated using KY Liquidand KY Jelly to understand whether the viscosity of these water-basedpersonal lubricants affected the lubricating properties of thehydrophilic and latex polymer blend coating.

It was noted that about 1.0 mL of KY liquid was required to wet theentire surface of the coating due to its higher viscosity compared towater, making it more challenging to be evenly distribute on the condomsurface. When comparing the slipperiness between the hydrophilic andlatex polymer blend-coated condoms with about 0.5 mL of KY Liquidcompared to non-lubricated condoms with about 0.5 mL of KY liquid viatouch, similar slipperiness and lubricating properties after 10-15 rubswere found. The slipperiness from the non-lubricated condom with KYliquid began to wear away after 15 rubs, resulting in higher frictionalforces, whereas the hydrophilic and latex polymer blend-coated condomwith KY Liquid maintained similar slipperiness even up to about 40-50rubs. We reasoned the aqueous properties of KY liquid could activate theHGCoat_2 similarly to water since no differences in slipperiness wasobserved between lubricating the condom with water or KY liquid. Furtherfrictional studies and investigations were pursued using a malemasturbator in addition to analyzing the effects of silicone-basedpersonal lubricants, which is described as followed.

To compare the hydrophilic and latex polymer blend coating lubricationdurability to commercially available personal lubricants and lubricatedcondoms, a male masturbator (Fleshlight) was used as an insertiondevice. Condoms were placed on a glass mandrel attached to a push/pullforce spring scale where frictional forces were recorded after every 10insertions (FIG. 4). All studies were conducted with 500 insertions intothe device with 0.5 mL of water added after every 50 insertions. Studieswere terminated when condoms broke.

The lubricating properties and coating durability of the hydrophilic andlatex polymer blend coating were compared to standard Durex, Lifestyles,and Trojan silicone-lubricated condoms. As a control, a non-lubricatedcondom with about 0.5 mL of water broke within about 10 insertions dueto high frictional forces between the latex and device interface (FIG.5; Grey Triangle (1)). As seen in FIG. 4, all three silicone-lubricatedcondoms (purple, red, orange) showed increasing frictional forces andbroke before 100 insertions. Contrastingly, HGCoat_2 condoms (blue)maintained consistently low frictional forces into the device even up to500 insertions. These results indicate that the hydrophilic and latexpolymer blend-coated condoms offer longer-lasting condom lubricitycompared to commercially available silicone-lubricated condoms.

Next, studies were conducted comparing the performance of thehydrophilic and latex polymer blend-coated condoms (green) tonon-lubricated (grey) condoms with about 0.5 mL of a silicone lubricant(Astroglide), water-based lubricant (KY Liquid), and water.Non-lubricated condoms with silicone-lubricant (FIG. 5; labeled“silicone-lubricated condom”) broke after 120 insertions whilenon-lubricated condoms with water-lubricant also broke after 170insertions (FIG. 5; labeled “Weer-based-lubricated condom”). It wasreasoned that the addition of water diluted these lubricants on thecondom surface, which similarly occurs to personal lubricants underphysiological conditions when exposed to the bodily fluids. Even higherfrictional forces were measured when repeating studies without rewettingsamples after every 50 insertions, as expected. In contrast, thehydrophilic and latex polymer blend-coated condoms FIG. 5; labeled“Water-based-lubricated HG-coated condom”; green boxes) lubricated with0.5 mL KY liquid could maintain low frictional forces similarly to thehydrophilic and latex polymer blend-coated condoms lubricated with water(FIG. 5; labeled “HG-coated condom”; green). Both demonstrated improvedperformance and its ability to offer longer-lasting condom lubricity.When repeating the study without rewetting the hydrophilic and latexpolymer blend-coated condom after every 50 insertions, its performancewas comparable to that of silicone-lubricated condoms. Additionally, itwas noted that adding silicone-lubricant to the hydrophilic and latexpolymer blend-coated condoms resulted in a similar lubricatingproperties and performance to commercially available silicone-lubricatedcondoms and non-lubricated condoms supplemented with a silicone personallubricant.

As noted in FIG. 6, SEM images of non-coated latex samples (FIG. 6A)depict a smooth surface while the HGCoat_2 coating on the latex wasobserved to result in a slightly rougher surface (FIG. 613). Thisobservation was confirmed via. AFM images when samples were imaged dryand with water. When imaging the surface via SEM through different partsof one condom and between different condoms, even coatings were noted,indicating the consistently and reproducibility within the hydrophilicand latex polymer blend coating. After rubbing the hydrophilic and latexpolymer blend coating samples several times with water, the coatingstill remained on the surface.

These results demonstrated that the hydrophilic and latex polymerblend-coated condoms offer durable and longer-lasting condom lubricitycompared to commercially available personal lubricants when in thepresence of minimal water or aqueous fluids.

The Hydrophilic and Latex Polymer Blend Coatings are Non-Cytotoxic

To determine whether the hydrophilic and latex polymer blend coating hadcytotoxic leachables, a standard cytotoxicity assay was conducted usinga fibroblast cell line (L cell, L-929; ATTC CCL-1) in accordance withISO 10993-5 (Microchem Laboratory; Round Rock, Tex.). In summary, thecell line was cultured in 24-well trays. Positive and negative controlswere prepared in addition to the hydrophilic and latex polymerblend-coated and non-coated latex test samples (n=4), which were allsterilized by autoclaving. All samples were directly exposed and were incontact with the cell monolayer for 24 hours at 37° C. After incubation,test samples were removed and aliquots from the media were placed inculture vessels afterwards, which were cultured for another 24 hours.Cells were analyzed to evaluate any changes in the morphology, celllysis, or destruction of the monolayer and were graded on a 0-4 scalecorrelating to no cytotoxicity (0; negative control) to severecytotoxicity (4; positive control).

Since latex is cytotoxic due to its hydrophobic and fouling surfaceproperties, the non-coated latex control and positive control both rated4, correlating to severe cytotoxicity. The hydrophilic and latex polymerblend-coated samples were graded with a 2, correlating to mildcytotoxicity in respect to the controls, implying the hydrophilic andlatex polymer blend coating reduces the cytotoxicity of the surfacecompared to non-coated latex.

Packaging Strategies with Rolled-Up Hydrophilic and Latex PolymerBlend-Coated Condoms

In the standard GMP manufacturing process, condoms are typicallypowdered lightly (to ensure the latex does not stick to itself whenpackaged), rolled up, and packaged with ˜0.5 mL of silicone lubricantprior to sealing the final product in an airtight foil. Variouspackaging strategies with and without lubricants and powders or dustingagents to ensure packaging hydrophilic and latex polymer blend-coatedcondoms are compatible under these conditions.

Samples were rolled up from glass mandrels after adding differentpowders or dusting agents (e.g., corn starch, baby power/talc) orpersonal lubricants (e.g., silicone- or water-based products) to thesurface. Six packaging samples investigated which included (I) nolubricant/powers (control); (2) 0.5 mL (standard) of silicone lubricant;(3) 0.5 mL of water-based lubricant; (4) water; (5) corn starch to thesurface; and, (6) baby powder to the surface. Also explored waslubricating and applying powders or dusting agents to the inside and/oroutside of condoms. All test samples (n=3) were wrapped in foil andpackaged in an airtight bag at room temperature. FIG. 7 shows an exampleof a rolled up and packaged condom with baby powder. After 7 days, toanalyzing the samples, condoms were unrolled and confirmed thelubricant/powders or dusting agents remained on the condom surface afterunrolling via visual inspection. Sample were wetted with 0.5 mL of waterand rubbed with fingers to determine whether the lubricants, powders, ordusting agents altered the coating's lubricating properties.

As expected, condoms packaged without lubricants or powders (control)were challenging to unroll as the latex adhered to itself. Samplespackaged with powders, both cornstarch and baby powder on the inside andoutside of condoms, were easily unrolled and the hydrophilic and latexpolymer blend-coated surface was slippery with water. Samples packagedwith water or the water-based lubricant resulted in sticky surfaces whenthe condom was unrolled, suggesting these lubricants are incompatiblefor condom packaging. This observation was consistent with currentcondom packaging standards since water-based lubricants are typicallyavoided for packaging, which can promote bacterial growth.

Silicon-lubricated hydrophilic and latex polymer blend-coated condomswere challenging to roll-up for packaging due to the slippery nature ofthe lubricant. After unrolling the samples, the silicone lubricant wasvisually present on the surface. However when wetting the hydrophilicand latex polymer blend-coated surface with water, it was observed aminor reduction in lubricating properties of the hydrophilic and latexpolymer blend coating. The hydrophobic silicone lubricant appeared tohave prevented water and water-based lubricants to be in contact withthe condom surface. After rubbing the silicone lubricant off the condomwith clean fingers to resemble the silicone lubricant wearing awayduring intercourse, the coating was fully lubricated and slippery withwater, making this a viable option for packaging. Additionally, weexplored packing hydrophilic and latex polymer blend-coated condoms withpowdered on the surface prior to the addition of silicon lubricantsimilarly to the standard packaging processes, which resulted in similarfindings.

Applicant's disclosure is described herein in preferred embodiments withreference to the Figures, in which like numbers represent the same orsimilar elements. Reference throughout this specification to “oneembodiment,” “an embodiment,” or similar language means that aparticular feature, structure, or characteristic described in connectionwith the embodiment is included in at least one embodiment of thepresent invention. Thus, appearances of the phrases “in one embodiment,”“in an embodiment,” and similar language throughout this specificationmay, but do not necessarily, all refer to the same embodiment.

The described features, structures, or characteristics of Applicant'sdisclosure may be combined in any suitable manner in one or moreembodiments. In the description, herein, numerous specific details arerecited to provide a thorough understanding of embodiments of theinvention. One skilled in the relevant art will recognize, however, thatApplicant's composition and/or method may be practiced without one ormore of the specific details, or with other methods, components,materials, and so forth. In other instances, well-known structures,materials, or operations are not shown or described in detail to avoidobscuring aspects of the disclosure.

In this specification and the appended claims, the singular forms “a,”“an,” and “the” include plural reference, unless the context clearlydictates otherwise.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art. Although any methods and materials similar or equivalent tothose described herein can also be used in the practice or testing ofthe present disclosure, the preferred methods and materials are nowdescribed. Methods recited herein may be carried out in any order thatis logically possible, in addition to a particular order disclosed.

INCORPORATION BY REFERENCE

References and citations to other documents, such as patents, patentapplications, patent publications, journals, books, papers, webcontents, have been made in this disclosure. All such documents arehereby incorporated herein by reference in their entirety for allpurposes. Any material, or portion thereof, that is said to beincorporated by reference herein, but which conflicts with existingdefinitions, statements, or other disclosure material explicitly setforth herein is only incorporated to the extent that no conflict arisesbetween that incorporated material and the present disclosure material.In the event of a conflict, the conflict is to be resolved in favor ofthe present disclosure as the preferred disclosure.

EQUIVALENTS

The representative examples are intended to help illustrate theinvention, and are not intended to, nor should they be construed to,limit the scope of the invention. Indeed, various modifications of theinvention and many further embodiments thereof, in addition to thoseshown and described herein, will become apparent to those skilled in theart from the full contents of this document, including the examples andthe references to the scientific and patent literature included herein.The examples contain important additional information, exemplificationand guidance that can be adapted to the practice of this invention inits various embodiments and equivalents thereof.

1-55. (canceled)
 56. A method for manufacturing a condom, comprising:providing a sheath of an elastomeric material selected from natural orsynthetic rubber latex, the sheath having an outer surface and an innersurface; depositing a first layer of an aqueous suspension of a latexpolymer to at least a portion of the outer surface of the sheath; curingthe latex polymer with exposure to heat for a time sufficient to form afirst or base layer of cured latex polymer; depositing a second layer ofa composition, comprising a hydrophilic polymer and a suspension oflatex polymer, to at least a portion of the first or base layer; andcuring the second layer of hydrophilic polymer and latex polymer withexposure to heat for a time sufficient to form a second or top layer,wherein the hydrophilic polymer has a mean molecular weight in the rangefrom about 1 kDa to about 1,000 kDa and is present in the composition ata concentration from about 2 w/v % to about 10 w/v %; the latex polymermicroparticles are present in the composition at a concentration fromabout 20 w/v % to about 60 w/v %; and the weight ratio of thehydrophilic polymer to the latex polymer microparticles is in the rangefrom about 1:1 to about 10:1.
 57. The method of claim 56, furthercomprising: depositing a third or top layer of a composition, comprisinga hydrophilic polymer and a suspension of latex polymer, to at least aportion of the second layer; and curing the third layer of hydrophilicpolymer and latex polymer with exposure to heat for a time sufficient toform a third or top layer.
 58. The method of claim 56, wherein at leasta portion of the outer surface, the first or base layer, or the secondlayer, is substantially all of the outer surface, the first or baselayer or the second layer, respectively.
 59. The method of claim 56,wherein curing the latex polymer is conducted at a temperature betweenabout 25° C. to about 70° C. for a time period from about 5 to about 60minutes.
 60. The method of claim 56, wherein curing the hydrophilicpolymer and a suspension of latex polymer is conducted at a temperaturebetween about 25° C. to about 70° C. for a time period from about 5 toabout 60 minutes.
 61. The method of claim 56, wherein the first or baselayer has a thickness in the range from about 0.01 mm to about 1.0 mm.62. The method of claim 56, wherein the first or base layer has athickness less than about 1.0 mm.
 63. The method of claim 61, whereinthe second, or the third if present, or top layer has a thickness in therange from about 0.01 mm to about 1.0 mm.
 64. The method of claim 61,wherein the second, or the third if present, or top layer has athickness less than about 1.0 mm.